H*ads dynamics engineering via bimetallic Pd-Cu@MXene catalyst for enhanced electrocatalytic hydrodechlorination.

Electrocatalytic hydrodechlorination (EHDC) is a promising approach to safely remove halogenated emerging contaminants (HECs) pollutants. However, sluggish production dynamics of adsorbed atomic H (H*ads) limit the applicability of this green process. In this study, bimetallic Pd-Cu@MXene catalysts were synthesized to achieve highly efficient removal of HECs. The alloy electrode (Pd-Cu@MX/CC) exhibited better EHDC performance in comparison to Pd@MX/CC electrode, resulting in diclofenac degradation efficiency of 93.3 ± 0.1%. The characterization analysis revealed that the Pd0/PdII ratio decreased by forming bimetallic Pd-Cu alloy. Density functional theory calculations further demonstrated the electronic configuration modulation of the Pd-Cu@MXene catalysts, optimizing binging energies for H* and thereby facilitating H*ads production and tuning the reduction capability of H*ads. Noteably, the amounts and reduction potential of H*ads for Pd-Cu@MXene catalysts were 1.5 times higher and 0.37 eV lower than those observed for the mono Pd electrode. Hence, the introduction of Cu into the Pd catalyst optimized the dynamics of H*ads production, thereby conferring significant advantages to EHDC reactions. This augmentation was underscored by the successful application of the alloy catalysts supported by MXene in EHDC experiments involving other HECs, which represented a new paradigm for EHDC for efficient recalcitrant pollutant removal by H*ads.

Atomic hydrogen-mediated enhanced electrocatalytic hydrodehalogenation on Pd@MXene electrodes.

In this study, a Pd@MXene catalyst was synthesized to enhance the electrocatalytic hydrodehalogenation (ECH) of emerging halogenated organic pollutants (HOPs) by improving the dispersibility, catalytic activity, and stability of palladium (Pd). The average size of Pd nanoparticles (NPs) was reduced to 3.62 ± 0.34 nm with a more intensive peak of Pd (111), which facilitated atomic hydrogen (H*) production. The Pd@MX/CC electrode demonstrated superior ECH activity for diclofenac (DCF) degradation, with a reaction rate constant (kobs) 2.48 times higher than that of Pd/CC (without MXene). The satisfactory ECH performance of Pd@MX/CC remained consistent within a wide range of initial DCF concentrations (5-100 mg/L), and no significant ECH attenuation was observed even after up to 10 batches. Furthermore, the high activity of Pd@MX/CC was also observed in the ECH of other halogenated organic pollutants (levofloxacin, tetrabromobisphenol A, and diatrizoate). Density functional theory (DFT) calculations revealed that electronic configuration modulation of the Pd@MXene catalyst optimized binging energies to H* , DCF, and dechlorinated products, thereby enhancing the ECH efficiency of DCF.

Non-radical mechanism and toxicity analysis of ß-cyclodextrin functionalized biochar catalyzing the degradation of bisphenol A and its analogs by peroxydisulfate.

Bisphenols (BPs) are distributed in worldwide as typical environmental hormones, which potentially harm the ecological environment and human health. In this study, four BPs, i.e., bisphenol A, bisphenol F, bisphenol S, and bisphenol AF, were used as prototypes to identify the intrinsic differences in degradation mechanisms correlated with the molecular structures in peroxydisulfate (PDS)-based advanced oxidation processes (AOPs). Electron transfer was the main way of modified biochar to trigger the heterogenous catalysis of PDS, which can cause the degradation of BPs. Phenolic hydroxyl groups on bisphenol pollutants were considered as possible active sites, and the existence of substituents was the main reason for the differentiation in the degradation efficiency of various bisphenols. Results of ecotoxicity prediction showed that most intermediates produced by the degradation of BPs in the ß-SB/PDS system, which was dominated by the electron transfer pathway, had a lower toxicity than the parent molecules, while the toxicity of several ring cleavage intermediates was higher. This study presents a simple modification scheme for the conversion of biochar into functional catalysts and provides insights into the mechanism of heterogeneous catalytic degradation mediated by modified biochar as well as the degradation differences of bisphenol pollutants and their potential ecotoxicity.